In recent years, fluorotelomer-based polymers (FTPs) have been the dominant product of the fluorotelomer industry. For the last decade, whether FTPs degrade to toxic perfluorocarboxylates (PFCAs) has been vigorously contested, with early studies arguing that FTPs have half-lives >1000 years, and others concluding decadal half-lives. Given this FTP half-life discrepancy of 10- to >100-fold, here we investigate whether environmental loads of long-chain PFCAs might offer an independent approach to assess FTP half-lives. Specifically we: i) use surface soil-PFCA data to estimate terrestrial surface-soil background PFCA concentrations and loads; ii) extrapolate these data to generate global PFCA load estimates; iii) compare these estimates to published ocean-derived and industrial-emissions load estimates, finding agreement for perfluorooctanoate (C8), but an excess in longer-chain (C10,C12) PFCAs for ocean- and soil-derived loads relative to emissions; iv) model FTP degradation rates required to reconcile this discrepancy; and iv) compare our modeled estimates to existing experimental results. These findings show agreement for FTP half-lives at the decades-scale supporting existing laboratory studies that report decade-scale half-lives for FTPs. This suggests that global long-chain PFCA loads will increase for decades if legacy FTPs already manufactured are not contained upon disposal. These results suggest that FTPs comprised of novel poly- and perfluorinated alkyl substances (PFASs) now in production might constitute considerable sources to the environment of the new generation of PFASs.

Interest and concern about polyfluorinated compounds (PFCs), such as perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and an increasing number of other related compounds is growing as more is learned about these ubiquitous anthropogenic substances. Many of these compounds can be toxic, and they are regularly found in the blood of animals and humans worldwide. A great deal of research has been conducted in this area, but a surprising amount remains unknown about their distribution in the environment and how people ultimately become exposed. The utility of these compounds seems to ensure their continued use in one form or another for the foreseeable future, presenting a long-term challenge to scientists, industry leaders, and public health officials worldwide.

ADVERTISEMENT RETURN TO ISSUEGuest CommentNEXTGuest Comment: Perfluoroalkyl Acid Focus IssueAndrew B. Lindstrom†*, Mark J. Strynar†, E. Laurence Libelo‡, and Jennifer A. Field§View Author Information† U.S. Environmental Protection Agency, National Exposure Research Laboratory, Research Triangle Park, North Carolina 27711, United States‡ U.S. Environmental Protection Agency, Office of Pollution Prevention and Toxics, Washington, D.C. 20460, United States§ Department of Environmental and Molecular Toxicology, Oregon State University, Corvallis, Oregon 97331, United StatesPhone: 919-541-0551; fax: 919-541-0905; e-mail: [email protected]Cite this: Environ. Sci. Technol. 2011, 45, 19, 7951–7953Publication Date (Web):September 29, 2011Publication History Published online29 September 2011Published inissue 1 October 2011https://pubs.acs.org/doi/10.1021/es202963phttps://doi.org/10.1021/es202963peditorialACS PublicationsCopyright © 2011 American Chemical Society. This publication is available under these Terms of Use. Request reuse permissions This publication is free to access through this site. Learn MoreArticle Views2316Altmetric-Citations28LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail PDF (2 MB) Get e-AlertscloseSUBJECTS:Alkyls,Materials,Toxicity Get e-Alerts

Perfluorinated chemicals (PFCs) such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) have been produced and used in a wide range of industrial and consumer products for many decades. Their resistance to degradation has led to their widespread distribution in the environment, but little is known about how humans become exposed. Recent studies have demonstrated that the application of PFC contaminated biosolids can have important effects on local environments, ultimately leading to demonstrable human exposures. This manuscript describes a situation in Decatur, Alabama where PFC contaminated biosolids from a local municipal wastewater treatment facility that had received waste from local fluorochemical facilities were used as a soil amendment in local agricultural fields for as many as twelve years. Ten target PFCs were measured in surface and groundwater samples. Results show that surface and well water in the vicinity of these fields had elevated PFC concentrations, with 22% of the samples exceeding the U.S. Environmental Protection Agency's Provisional Health Advisory level for PFOA in drinking water of 400 ng/L. Water/soil concentration ratios as high as 0.34 for perfluorohexanoic acid, 0.17 for perfluoroheptanoic acid, and 0.04 for PFOA verify decreasing mobility from soils with increasing chain length while indicating that relatively high transport from soils to surface and well water is possible.

Sludges generated at a wastewater treatment plant (WWTP) in Decatur, Alabama have been applied to agricultural fields for more than a decade. Waste-stream sources to this WWTP during this period included industries that work with fluorotelomer compounds, and sludges from this facility have been found to be elevated in perfluoroalkylates (PFAs). With this knowledge, the U.S. Environmental Protection Agency collected soil samples from sludge-applied fields as well as nearby "background" fields for PFA analysis. Samples from the sludge-applied fields had PFAs at much higher concentrations than in the background fields; generally the highest concentrations were perfluorodecanoic acid (≤ 990 ng/g), perfluorododecanoic acid (≤ 530 ng/g), perfluorooctanoic acid (≤ 320 ng/g), and perfluorooctane sulfonate (≤ 410 ng/g). Contrasts in PFA concentration between surface and deeper soil samples tended to be more pronounced in long-chain congeners than shorter chains, perhaps reflecting relatively lower environmental mobilities for longer chains. Several PFAs were correlated with secondary fluorotelomer alcohols (sec-FTOHs) suggesting that PFAs are being formed by degradation of sec-FTOHs. Calculated PFA disappearance half-lives for C6 through C11 alkylates ranged from about 1 to 3 years and increase with increasing chain-length, again perhaps reflecting lower mobility of the longer-chained compounds.

The environmental prevalence of a new class of perfluorinated acids, the perfluorinated phosphonic acids ( PFPA s), was determined in Canadian surface waters and wastewater treatment plant (WWTP) effluent. For quality control and comparison, the C8‐ to C11‐perfluorinated carboxylic acids and perfluorooctane sulfonic acid were included in the analysis. Water samples were extracted using weak anion‐exchange solid‐phase extraction cartridges. Perfluorinated phosphonic acids were observed in 80% of surface water samples and in six of the seven WWTP effluent samples. The C8‐PFPA was observed at concentrations ranging from 88 ± 33 to 3,400 ± 900 pg/L in surface waters and from 760 ± 270 to 2,500 ± 320 pg/L in WWTP effluent. To our knowledge, this is the first observation of PFPAs in the environment. Given their structural similarities with perfluorinated carboxylic and sulfonic acids, PFPAs are expected to be persistent. The observation of PFPAs in the majority of samples analyzed here suggests they are prevalent environmental contaminants and should be considered in future environmental monitoring campaigns to better understand the total burden of fluorinated materials in the environment.

Sources of human exposure to perfluorinated carboxylic acids (PFCAs) are not well-characterized. Polyfluoroalkyl phosphoric acids (PAPs) are fluorinated surfactants used in human food contact paper products. PAPs can migrate into food and food simulants, and their bioavailability and biotransformation into PFCAs has been demonstrated using a rat model. To characterize human exposure to PAP materials, we analyzed pooled human sera samples collected in 2004 and 2005 (n = 10) and 2008 (n = 10) from the midwestern United States for the 4:2 through 10:2 PAP diesters (diPAPs). The 2004 and 2005 sera samples contained 4.5 mu g/L total diPAPs, with the 6:2 diPAP dominating the congener profile at 1.9 +/- 0.4 mu g/L DiPAP concentrations observed in the 2004 and 2005 human sera samples were similar to those of the C8 to C11 PFCAs (0.13 +/- 0.01 to 4.2 +/- 0.3 mu g/L) monitored in the same samples. 6:2 diPAP was also consistently observed in the 2008 human sera samples at a mean concentration of 0.63 +/- 0.13 mu g/L. As diPAPs have been shown to degrade to PFCAs; in vivo, our observation of diPAPs in human sera may be a direct connection between the legacy of human PFCA contamination and PAPs commercial applications. Wastewater treatment plant (WWTP) sludge and paper fibers were analyzed for diPAPs as a proxy for human use and potential exposure to diPAPs. DiPAPs were observed in WWTP sludge at concentrations ranging from 47 +/- 22 to 200 +/- 130 ng/g, a range similar to perfluorooctane sulfonic acid (PFOS) (100 +/- 70 ng/g) and greater than the C8 to C11 PFCAs (1.6 +/- 0.6 to 0.17 +/- 0.10 ng/g) observed in the same samples. DiPAPs were observed in paper fiber extracts at concentrations ranging from 34 +/- 30 to 2200 +/- 400 ng/g. The high diPAP concentrations in WWTP sludge suggest PAP materials may be prevalent in our daily lives.

A fast, rigorous method was developed to maximize the extraction efficacy for ten perfluorocarboxylic acids and perfluorooctanesulfonate from waste-water-treatment sludge and to quantitate using liquid chromatography, tandem-mass spectrometry (LC/MS/MS). First, organic solvents were tested for extraction efficiency, including acetonitrile (ACN), methanol (MeOH), isopropanol (IPA), tetrahydrofuran (THF), and 50/50 ACN/MeOH (v/v). Among the extractants tested, 50/50 ACN/MeOH yielded the best results for our combined criteria of extraction efficacy and solvent-handling convenience. Second, chemical pretreatment prior to solvent extraction was tested with sodium hydroxide (NaOH), potassium hydroxide (KOH), hydrochloric acid (HCl), and potassium persulfate (K2S2O8). Pretreatment with NaOH and HCl effectively recovered additional PFCs from the sludge, but KOH and K2S2O8 digestion were less effective than no pretreatment. Third, cleanup methods were investigated with solid-phase extraction using HLB (hydrophilic–lipophilic balanced) and WAX (weak-anion exchange) stationary phases, and with ion-pairing. The HLB stationary phase yielded a slight edge over the other two cleanup strategies in terms of recoverable PFCs and chromatographic separation. Finally, the appropriateness of isotopically labeled PFCs for quantitating unlabeled PFCs using isotopic dilution in complex sludge extracts was evaluated by comparison to results obtained with the standard-addition method. A National Institute of Standards and Technology (NIST) domestic sludge (CRM 2781) was analyzed using our finalized method and compared with previously reported results.

The occurrence of perfluorinated compounds (PFCs) in human blood is known to be widespread; nevertheless, the sources of exposure to humans, including infants, are not well understood. In this study, breast milk collected from seven countries in Asia was analyzed (n=184) for nine PFCs, including perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA). In addition, five brands of infant formula (n=21) and 11 brands of dairy milk (n=12) collected from retail stores in the United States were analyzed, for comparison with PFC concentrations previously reported for breast milk from the U.S. PFOS was the predominant PFC detected in almost all Asian breast milk samples, followed by perfluorohexanesulfonate (PFHxS) and PFOA. Median concentrations of PFOS in breast milk from Asian countries varied significantly;the lowest concentration of 39.4 pg/mL was found in India, and the highest concentration of 196 pg/mL was found in Japan. The measured concentrations were similarto or less than the concentrations previously reported from Sweden, the United States, and Germany (median, 106-166 pg/mL). PFHxS was found in more than 70% of the samples analyzed from Japan, Malaysia, Philippines, and Vietnam, at mean concentrations ranging from 6.45 (Malaysia) to 15.8 (Philippines) pg/mL PFOA was found frequently only in samples from Japan; the mean concentration for that country was 77.7 pg/mL. None of the PFCs were detected in the infant-formula or dairy-milk samples from the U.S. except a few samples that contained concentrations close to the limit of detection. The estimated average daily intake of PFOS by infants from seven Asian countries, via breastfeeding, was 11.8 +/- 10.6 ng/kg bw/ day; this value is 7-12 times higher than the estimated adult dietary intakes previously reported from Germany, Canada, and Spain. The average daily intake of PFOA by Japanese infants was 9.6 +/- 4.9 ng/kg bw/day, a value 3-10 times greater than the estimated adult dietary intakes reported from Germany and Canada. The highest estimated daily intakes of PFOS and PFOA by infants from seven Asian countries studied were 1-2 orders of magnitude below the tolerable daily intake values recommended by the U.K. Food Standards Agency.

The relative importance of jet fuel biodegradation relative to the respiration of natural organic matter in a contaminated organic-rich aquifer underlying a fire training area at Tyndall Air Force Base, Florida, USA was determined with isotopic measurements. Thirteen wells were sampled and analyzed for BTX (benzene, toluene, xylene), dissolved inorganic carbon (DIC) and CH4 concentrations, and delta13C and 14C of DIC. Results range from non-detectable to 3790 ppb, 1.4-24 mM, 0.2-776 microM, +5.8 per thousand to -22 per thousand, and from 52 to 99 pmc, respectively. Residual fuel was confined to two center wells underlying the fire training area. DIC and CH4 concentrations were elevated down-gradient of the contamination, but also at sites that were not in the apparent flow path of the contaminated groundwater. DIC exhibited greatest delta13C enrichment at highest DIC and CH4 concentrations indicating that CH4 production was an important respiration mode. Radiocarbon-depleted DIC was observed at sites with high hydrocarbon concentrations and down-gradient of the site. The results indicate that while natural attenuation was not rapidly reducing the quantity of free product overlying the aquifer at the site of contamination, it was at least constraining its flow away from the spill site. Apparently under the conditions of this study, BTX was degraded as rapidly as it was dissolved.

The controlled release of a mixture simulating jet fuel was conducted to determine the effects of transport and degradation on the δ13C of reactants and products in a field setting. Benzene, toluene, naphthalene, xylenes, and decane were mixed with native soil and placed 4 m below ground into a surficial aquifer. The δ13C values of the hydrocarbons prior to and after emplacement were measured and no significant isotopic fractionation was observed following migration and partial degradation. The δ13C values of the compounds within the hydrocarbon mixture prior to addition and following 40 and 164 days in the field ranged from −26.6 to −30.0, −26.3 to −30.4 and −26.5 to −29.4‰, respectively. Also measured were the concentrations and δ13C values of respiration endproducts CO2 and CH4 in groundwater samples prior to and 164, 278, 468, 642 and 831 days after the contamination of the surficial aquifer. Endproduct concentrations were clearly elevated relative to pre-emplacement values indicating microbial respiration of the added hydrocarbon mixture. Isotope mass balance calculations yielded similar δ13C values for the sum of the respiration products and the added hydrocarbon mixture. Our results indicate that the products of hydrocarbon respiration reflect the δ13C of the substrates, and in less controlled contaminated field settings DIC isotopic values may be useful for estimating hydrocarbon degradation when DIC up-gradient of the spill has a δ13C value different from that of the contaminants.

Subsurface hydrocarbon contamination associated with petroleum spills is a widespread occurrence that presents a significant threat to groundwater resources. The natural attenuation test site (NATS) at Columbus Air Force Base, MS, provided a unique opportunity to monitor changes in the molecular microbial ecology as well as stimulation of natural biodegradative processes under transient field study conditions. A large, synthetic jet fuel mixture containing BTEX compounds and naphthalene in a decane carrier was introduced into the subsurface. Over 462 days, a plume of hydrocarbon contamination developed and stabilized at a distance of less than 15 m downgradient from the source area. Exposure of indigenous microorganisms to the contaminant hydrocarbons was evaluated using an array of gene probes targeting common genotypes associated with the aerobic biodegradation of BTEX and naphthalene. Each of the targeted genotypes alkB, nahA, nahH, todC1C2, and xylA showed significant responses to hydrocarbon exposure. Aerobic mineralization potentials of selected contaminants were greater in sediments collected from within the plume relative to uncontaminated areas, suggesting that an aerobic contaminant-degrading community successfully developed within the plume. An increase in aerobic degradation activity coincided with the arrival of the hydrocarbon front within the well field. The Natural Attenuation Study at Columbus AFB successfully linked adaptations of indigenous microorganisms to hydrocarbon exposure during a transient field study.

In order to study the geochemical and biochemical processes which contribute to Natural Attenuation of hydrocarbons in ground water systems, a subsurface residual NAPL hydrocarbon mixture was emplaced in the heterogeneous aquifer at the Columbus AFB, MS groundwater test site. Changes in aqueous and aquifer solid geochemistry and microbiology, indicative of Natural Attenuation, are being monitored as the dissolved hydrocarbon plume is formed by groundwater flow under natural hydraulic gradients. Understanding the biogeochemisrty of the aquifer will allow a better understanding of mechanisms and rates of processes which contribute to Natural Attenuation. This, hopefully, will allow us to identify easily measured indicators Natural Attenuation, and produce a scientifically validate guides for implementation.

A test release of a model weathered jet fuel is being used to study the geochemical and biochemical processes that contribute to natural attenuation of hydrocarbons in groundwater. To study initial development and stabilization of a dissolved plume with known initial conditions a subsurface residual NAPL hydrocarbon mixture was emplaced in the well characterized and highly instrumented heterogeneous aquifer at the Columbus AFB, groundwater test site. Groundwater moving through the source zone under natural hydraulic gradients is dissolving the hydrocarbons and transporting the dissolved hydrocarbon plume downgradient. Background sampling of groundwater and aquifer solids was done prior to source emplacement to characterize the site geochemistry and the anaerobic and aerobic microbiology. Continued sampling is characterizing changes in redox conditions and microbiological numbers and diversities associated with natural attenuation, The dissolved hydrocarbon plume appears to have stabilized within a few weeks of emplacement, and microbial processes are limiting plume propagation to within 20 m downgradient from the source. Dissolved oxygen depletion, the formation of Fe2+ along with dissolved hydrogen and microbial evidence suggest that the plume has shifted from aerobic to anaerobic conditions near the source. Stable carbon isotope ratios confirm that microbial degradation is responsible for hydrocarbon attenuation. Observed natural attenuation is correlated with microbial and geochemical changes in the aquifer.